JP2010106263A - Filament-reinforced thermoplastic resin particle - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a filament-reinforced thermoplastic resin particle showing good openability of the reinforcing fiber at molding, having a good appearance, and producing a molded product having high mechanical strength. <P>SOLUTION: The filament-reinforced thermoplastic resin particle includes a thermoplastic resin produced by using a metallocene catalyst, a modified polyolefin resin obtained by modification with an unsaturated carboxylic acid or a derivative thereof, and a reinforcing fiber, and satisfies the following conditions (1) to (5): (1) the modified amount of an unsaturated carboxylic acid or a derivative thereof is 0.01-2 wt.% based on the total 100 wt.% of the thermoplastic resin and the modified polyolefin resin; (2) the content of the thermoplastic resin and the modified polyolefin resin is 20-70 wt.% based on the total 100 wt.% of the thermoplastic resin, the modified polyolefin resin and the reinforcing fiber; (3) the content of the reinforcing fiber is 30-80 wt.% based on the total 100 wt.% of the thermoplastic resin, the modified polyolefin resin and the reinforcing fiber; (4) the amount of acetaldehyde emitted from the filament-reinforced thermoplastic resin particle is &le;3.0 &mu;g/m<SP>3</SP>when 25 g of the filament-reinforced thermoplastic resin particle is left at 65&deg;C in a 20L sealed chamber for 1 hours; and (5) the melting point of the resin component in the filament-reinforced thermoplastic resin particle is &ge;150&deg;C. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to long fiber reinforced thermoplastic resin particles.

  Long fiber reinforced thermoplastic resin pellets are widely used as automotive module parts that require high strength as molded articles mixed with polyolefin resins for dilution. However, due to poor dispersion of the reinforcing fiber in the long fiber reinforced resin composition containing the long fiber reinforced thermoplastic resin pellet, the reinforcing fiber sometimes appears as a lump on the module component surface. For this reason, the module component obtained from this long fiber reinforced resin composition needs to be used as a component at a location where the level of appearance requirement is low, or the surface thereof must be coated.

In order to solve the above problems, a fiber reinforced resin composition having improved appearance of a molded product obtained has been reported (see Patent Documents 1 and 2).
However, a molded product obtained from the above-described fiber reinforced resin composition does not completely satisfy the high appearance required by, for example, automobile module parts, and further improvement in appearance has been demanded.

JP 2004-3000293 A JP 2006-193735 A

  The present invention provides long fiber reinforced thermoplastic resin particles that have a good fiber opening property during molding, an excellent appearance, and a molded product having high mechanical strength such as bending strength. Is an issue.

  As a result of intensive studies, the present inventors have found that when a thermoplastic resin, a modified polyolefin resin and a long fiber reinforced thermoplastic resin particle containing a reinforcing fiber produced using a metallocene catalyst are molded using the particle. In addition, the inventors have found that it is possible to provide a molded article having good fiber opening property, excellent appearance, and excellent mechanical strength, and thus completed the present invention.

That is, the present invention includes the following matters.
[1] A thermoplastic resin produced using a metallocene catalyst,
A long fiber reinforced thermoplastic resin particle comprising a modified polyolefin resin modified with an unsaturated carboxylic acid or a derivative thereof, and reinforcing fibers, and satisfying the following requirements (1) to (5).
(1) The amount of modification of the unsaturated carboxylic acid or derivative thereof is 0.01 to 2% by weight in a total of 100% by weight of the thermoplastic resin and the modified polyolefin resin.
(2) The thermoplastic resin and the modified polyolefin resin are contained in a total of 20 to 70% by weight in the total 100% by weight of the thermoplastic resin, the modified polyolefin resin and the reinforcing fiber.
(3) 30 to 80% by weight of reinforcing fiber is contained in 100% by weight of the total of the thermoplastic resin, modified polyolefin resin and reinforcing fiber.
(4) When 25 g of long fiber reinforced thermoplastic resin particles are sealed in a 20 L chamber and left at 65 ° C. for 1 hour, the amount of acetaldehyde released from the long fiber reinforced thermoplastic resin particles is 3.0 μg / m. ³ or less.
(5) The melting point of the resin component in the long fiber reinforced thermoplastic resin particles is 150 ° C. or higher.

  [2] A total of 100% by weight of the thermoplastic resin and the modified polyolefin resin contains 75 to 99% by weight of a thermoplastic resin and 1 to 25% by weight of a modified polyolefin resin. The long fiber reinforced thermoplastic resin particles described in 1.

[3] The long fiber reinforced thermoplastic as described in [1] or [2], wherein the thermoplastic resin satisfies the following requirements (a-1), (a-2) and (a-3): Resin particles.
(A-1) The melt index (MI; resin temperature 230 ° C., load 21.18 N) is in the range of 100 to 250 g / 10 minutes.
(A-2) The amount of components soluble in 90- ° C. o-dichlorobenzene measured by cross fractionation chromatography (CFC method) is 1% by weight or less.
(A-3) Molecular weight distribution (Mw / Mn) is less than 3.5.

  [4] Any one of [1] to [3], wherein the thermoplastic resin is at least one polymer selected from propylene homopolymer and propylene-α-olefin random copolymer. The long fiber reinforced thermoplastic resin particle according to claim 1.

  [5] A molded product obtained by molding using the long fiber reinforced thermoplastic resin particles according to any one of [1] to [4].

  ADVANTAGE OF THE INVENTION According to this invention, the long fiber reinforced thermoplastic resin particle which has the outstanding external appearance property and can obtain the molded object with high mechanical strength can be provided. That is, according to the present invention, it is possible to provide a molded article that has good fiber-opening properties in the injection cylinder at the time of molding, and that has less fiber lump found on the surface of the molded article. Furthermore, since this molded object does not generate a volatile organic compound (VOC), it is suitably used for automobile parts.

FIG. 1 is a schematic view of an apparatus for producing long fiber reinforced thermoplastic resin particles.

Hereinafter, the components constituting the long fiber reinforced thermoplastic resin particles (long fiber reinforced thermoplastic resin pellets) of the present invention will be described in detail.
<Thermoplastic resin>
As the thermoplastic resin according to the present invention, for example, polyolefin resin and polystyrene resin can be used. Specific examples of the polyolefin resin include polypropylene resins such as propylene homopolymer and propylene-α-olefin random copolymer, and 4-methyl-1-pentene polymer resin. Here, specific examples of the α-olefin include ethylene, 1-butene, 1-pentene, 1-hexene and 1-octene, and particularly preferably includes ethylene and butene. The α-olefin may be used alone or in combination of two or more. Among these, a polypropylene resin is preferable in terms of moldability and heat resistance, and a propylene homopolymer is particularly preferable. Specific examples of the polystyrene-based resin include syndiotactic polystyrene.

  As a method for producing a thermoplastic resin, a known production method using a metallocene catalyst containing a metallocene compound having a ligand having a cyclopentadienyl skeleton in the molecule is used. For example, WO 01/27124 is used. Production methods described in pamphlets and JP-A-11-315109 can be used. Examples of the metallocene compound include two kinds of metallocene compounds represented by the following general formula [I] and a bridged metallocene compound represented by the following general formula [II] because of its chemical structure. Among these, a bridged metallocene compound is preferable.

上記一般式［Ｉ］および［ＩＩ］において、Ｍはチタン原子、ジルコニウム原子またはハフニウム原子を示し、Ｑはハロゲン原子、炭化水素基、アニオン配位子および孤立電子対で配位可能な中性配位子から選ばれる基であり、ｊは１〜４の整数であり、Ｃｐ¹およびＣｐ²は、シクロペンタジエニル基または置換シクロペンタジエニル基であり、互いに同一でも異なっていてもよく、Ｍを挟んだサンドイッチ構造を形成する。ここで、置換シクロペンタジエニル基とは、インデニル基、フルオレニル基、アズレニル基またはこれらの基にハイドロカルビル基またはケイ素含有基が一つ以上置換した基であり、置換シクロペンタジエニル基がインデニル基、フルオレニル基またはアズレニル基である場合、シクロペンタジエニル基に縮合する不飽和環の二重結合の一部は水添されていてもよい。一般式［ＩＩ］において、Ｙは炭素原子数１〜２０の２価の炭化水素基、炭素原子数１〜２０の２価のハロゲン化炭化水素基、２価のケイ素含有基、２価のゲルマニウム含有基、２価のスズ含有基、-Ｏ-、-ＣＯ-、-Ｓ-、-ＳＯ-、-ＳＯ₂-、-Ｇｅ-、-Ｓｎ-、-ＮＲ^a-、-Ｐ(Ｒ^a)-、-Ｐ(Ｏ)(Ｒ^a)-、-ＢＲ^a-または-ＡｌＲ^a-を表す（ただし、Ｒ^aは、炭素原子数１〜２０の炭化水素基、炭素原子数１〜２０のハロゲン化炭化水素基、水素原子、ハロゲン原子、または窒素原子に炭素原子数１〜２０の炭化水素基が1個または２個結合した窒素化合物残基であり、互いに同一でも異なっていてもよい。）。

In the above general formulas [I] and [II], M represents a titanium atom, a zirconium atom, or a hafnium atom, and Q represents a neutral configuration that can be coordinated by a halogen atom, a hydrocarbon group, an anionic ligand, and a lone electron pair. A group selected from a ligand, j is an integer of 1 to 4, Cp ¹ and Cp ² are a cyclopentadienyl group or a substituted cyclopentadienyl group, and may be the same or different from each other; A sandwich structure sandwiching M is formed. Here, the substituted cyclopentadienyl group is an indenyl group, a fluorenyl group, an azulenyl group or a group obtained by substituting one or more of these groups with a hydrocarbyl group or a silicon-containing group. In the case of an indenyl group, a fluorenyl group or an azulenyl group, a part of the double bond of the unsaturated ring condensed to the cyclopentadienyl group may be hydrogenated. In the general formula [II], Y represents a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, and a divalent germanium. -Containing group, divalent tin-containing group, -O-, -CO-, -S-, -SO-, -SO _2- , -Ge-, -Sn-, -NR ^a- , -P (R ^a ) -, - P (O) ( R a) -, - BR a - or -AlR ^a - represents a (wherein, R ^a is a hydrocarbon group having 1 to 20 carbon atoms, halogen having 1 to 20 carbon atoms And a nitrogen compound residue in which one or two hydrocarbon groups having 1 to 20 carbon atoms are bonded to a hydrogen atom, a hydrogen atom, a halogen atom, or a nitrogen atom, which may be the same or different from each other. .

  Among the metallocene compounds preferably used in the present invention, among the bridged metallocene compounds represented by the above general formula [II], the present applicant has already disclosed the following general formula [III] disclosed in WO 01/27124. ] The bridge | crosslinking type metallocene compound represented by this. The polymerization catalyst used in the present invention is a compound capable of forming an ion pair by reacting with a crosslinked metallocene compound, an organometallic compound, an organoaluminum oxy compound and a metallocene compound represented by the general formula [III] Accordingly, the metallocene catalyst comprises a particulate carrier.

上記一般式［ＩＩＩ］において、Ｒ¹〜Ｒ¹⁴は各々独立に水素原子、炭化水素基およびケイ素含有基を表し、同一でも異なっていてもよい。ここで、炭化水素基としては、メチル基、エチル基、ｎ-プロピル基、アリル基、ｎ-ブチル基、ｎ-ペンチル基、ｎ-ヘキシル基、ｎ-ヘプチル基、ｎ-オクチル基、ｎ-ノニル基およびｎ-デカニル基などの直鎖状炭化水素基；イソプロピル基、ｔ-ブチル基、アミル基、3-メチルペンチル基、1,1-ジエチルプロピル基、1,1-ジメチルブチル基、1-メチル-1-プロピルブチル基、1,1-プロピルブチル基、1,1-ジメチル-2-メチルプロピル基および1-メチル-1-イソプロピル-2-メチルプロピル基などの分岐状炭化水素基；シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、ノルボルニル基およびアダマンチル基などの環状飽和炭化水素基；フェニル基、トリル基、ナフチル基、ビフェニル基、フェナントリル基およびアントラセニル基などの環状不飽和炭化水素基；ベンジル基、クミル基、1,1-ジフェニルエチル基およびトリフェニルメチル基などの環状不飽和炭化水素基で置換された飽和炭化水素基；メトキシ基、エトキシ基、フェノキシ基、フリル基、Ｎ-メチルアミノ基、Ｎ,Ｎ-ジメチルアミノ基、Ｎ-フェニルアミノ基、ピリル基およびチエニル基などのヘテロ原子含有炭化水素基などが挙げられる。ケイ素含有基としては、トリメチルシリル基、トリエチルシリル基、ジメチルフェニルシリル基、ジフェニルメチルシリル基およびトリフェニルシリル基などが挙げられる。また、Ｒ⁵〜Ｒ¹²のうち隣接する基は互いに結合して環を形成してもよい。Ｒ⁵〜Ｒ¹²を有する置換フルオレニル基としては、具体的には、ベンゾフルオレニル基、ジベンゾフルオレニル基、オクタヒドロジベンゾフルオレニル基、オクタメチルオクタヒドロジベンゾフルオレニル基およびオクタメチルテトラヒドロジシクロペンタフルオレニル基などが挙げられる。

In the general formula [III], R ^{1 to} R ¹⁴ each independently represent a hydrogen atom, a hydrocarbon group, or a silicon-containing group, and may be the same or different. Here, as the hydrocarbon group, methyl group, ethyl group, n-propyl group, allyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n- Linear hydrocarbon groups such as nonyl and n-decanyl; isopropyl, t-butyl, amyl, 3-methylpentyl, 1,1-diethylpropyl, 1,1-dimethylbutyl, 1 -Branched hydrocarbon groups such as methyl-1-propylbutyl, 1,1-propylbutyl, 1,1-dimethyl-2-methylpropyl and 1-methyl-1-isopropyl-2-methylpropyl; Cyclic saturated hydrocarbon groups such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl and adamantyl; phenyl, tolyl, naphthyl, biphenyl, phenanthryl and anthracenyl Cyclic unsaturated hydrocarbon groups of the above; saturated hydrocarbon groups substituted with cyclic unsaturated hydrocarbon groups such as benzyl, cumyl, 1,1-diphenylethyl and triphenylmethyl; methoxy, ethoxy, phenoxy And hetero atom-containing hydrocarbon groups such as a group, a furyl group, an N-methylamino group, an N, N-dimethylamino group, an N-phenylamino group, a pyryl group and a thienyl group. Examples of the silicon-containing group include a trimethylsilyl group, a triethylsilyl group, a dimethylphenylsilyl group, a diphenylmethylsilyl group, and a triphenylsilyl group. Moreover, adjacent groups among R ^{5 to} R ¹² may be bonded to each other to form a ring. Specific examples of the substituted fluorenyl group having R ^{5 to} R ¹² include benzofluorenyl group, dibenzofluorenyl group, octahydrodibenzofluorenyl group, octamethyloctahydrodibenzofluorenyl group and octamethyl. Examples thereof include a tetrahydrodicyclopentafluorenyl group.

In the general formula [III], R ^{1 to} R ⁴ substituted on the cyclopentadienyl ring are preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, more preferably R ² and R ⁴ are carbon atoms. A hydrocarbon group having 1 to 20 carbon atoms, particularly preferably R ¹ and R ³ are hydrogen atoms, and R ² and R ⁴ are linear or branched alkyl groups having 1 to 5 carbon atoms.

In the general formula [III], R ^{5 to} R ¹² substituted on the fluorene ring are preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Examples of the hydrocarbon group having 1 to 20 carbon atoms include the same hydrocarbon groups as those described above. Adjacent groups of R ^{5 to} R ¹² may be bonded to each other to form a ring, and R ^{6 to} R ⁷ and R ^{10 to} R ¹¹ are preferably a fluorene ring that is not a hydrogen atom at the same time.

In the general formula [III], Y which bridges the cyclopentadienyl ring and the fluorenyl ring is a Group 14 element, preferably a carbon atom, a silicon atom or a germanium atom, more preferably a carbon atom. R ^{13 to} R ¹⁴ substituted for Y are each independently a hydrocarbon group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 to 20 carbon atoms. More preferably a methyl group, an ethyl group, a phenyl group or a tolyl group. R ^{13 to} R ¹⁴ may be the same or different and may be bonded to each other to form a ring. R ^{13 to} R ¹⁴ may be bonded to an adjacent group among R ^{5 to} R ¹² or an adjacent group among R ^{1 to} R ⁴ to form a ring.

  In the general formula [III], M is a Group 4 transition metal, preferably a titanium atom, a zirconium atom or a hafnium atom. Q is a group selected from a halogen atom, a hydrocarbon group, an anionic ligand, and a neutral ligand capable of coordinating with a lone electron pair. j is an integer of 1 to 4, and when j is 2 or more, Qs may be the same or different from each other. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Specific examples of the hydrocarbon group include the same as those described above. Specific examples of anionic ligands include alkoxy groups such as methoxy, t-butoxy and phenoxy; carboxylate groups such as acetate and benzoate; sulfonate groups such as mesylate and tosylate. Specific examples of neutral ligands that can be coordinated by lone pairs include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, and diphenylmethylphosphine; tetrahydrofuran, diethyl ether, dioxane, and 1,2-dimethoxy And ethers such as ethane. At least one of Q is preferably a halogen atom or an alkyl group.

  Examples of the bridged metallocene compound preferably used in the present invention include dimethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, 1-phenylethylidene. (4-t-butyl-2-methylcyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, [3- (1 ′, 1 ′, 4 ′, 4 ′, 7 ′, 7 ′, 10 ', 10'-octamethyloctahydrodibenzo [b, h] fluorenyl) (1,1,3-trimethyl-5-t-butyl-1,2,3,3a-tetrahydropentalene)] zirconium dichloride Can be mentioned.

  A compound (cocatalyst) that forms an ion pair by reacting with an organometallic compound, an organoaluminum oxy compound, and a metallocene compound, which are used together with the metallocene compound represented by the general formula [III], and a particulate form used as necessary As the carrier, the compounds disclosed in the above-mentioned WO 01/27124 pamphlet and JP-A-11-315109 can be used without any particular limitation.

  In the production examples in the examples of the present invention described later, as the metallocene compound represented by the general formula [III], [3- (1 ′, 1 ′, 4 ′, 4 ′, 7 represented by the following formula (A)]: ', 7', 10 ', 10'-octamethyloctahydrodibenzo [b, h] fluorenyl) (1,1,3-trimethyl-5-t-butyl-1,2,3,3a-tetrahydropentalene) A propylene homopolymer is produced by prepolymerizing in the presence of zirconium dichloride and a solid catalyst in which methylaluminoxane as a cocatalyst is supported on a silica carrier and triethylaluminum, followed by multi-stage main polymerization.

重合方法としては、特に制限されないが、例えば、単独重合、共重合および多段重合などが用いられる。

Although it does not restrict | limit especially as a polymerization method, For example, homopolymerization, copolymerization, multistage polymerization, etc. are used.

  When a polypropylene resin is used as the thermoplastic resin according to the present invention, an elastomer may be added as necessary in the form of a polypropylene resin composition for the purpose of improving impact resistance. As the elastomer, propylene-α-olefin copolymers such as ethylene-α-olefin random copolymers, ethylene-α-olefin-nonconjugated polyene random copolymers, hydrogenated block copolymers, other elastic polymers, And a mixture thereof. As the α-olefin, those similar to those already described as the α-olefin constituting the polyolefin resin can be used, and may be used alone or in combination of two or more. Also good.

  Examples of the method for producing the polypropylene resin composition include a physical blending method, for example, a melt blending method. The melt blending method is a method of mechanical kneading while heating and plasticizing using a mixing roll, a Banbury mixer or a single or twin screw extruder.

  Further, when the polypropylene resin composition is composed of a polypropylene resin and a propylene-α-olefin copolymer, in addition to the production by a physical blend method, the polypropylene resin composition is produced in a production form of a propylene-α-olefin block copolymer. May be. Propylene-α-olefin block copolymer is produced by continuously performing the following two steps (Step 1 and Step 2).

[Step 1] Propylene and, if necessary, one or more olefins selected from ethylene and α-olefins having 4 or more carbon atoms are (co) polymerized in the presence of a metallocene compound-containing catalyst to produce a propylene homopolymer or propylene -The process of manufacturing an alpha olefin copolymer.
[Step 2] Propylene and one or more olefins selected from ethylene and an α-olefin having 4 or more carbon atoms are copolymerized in the presence of a metallocene compound-containing catalyst to produce ethylene and an α-olefin having 4 or more carbon atoms. The process of manufacturing the propylene-alpha-olefin copolymer contained more than one.

As the thermoplastic resin according to the present invention, the above-mentioned resins may be used alone or in combination of two or more.
The melting point of the resin component in the long fiber reinforced thermoplastic resin particles is 150 ° C. or higher, preferably 150 to 163 ° C., more preferably 156 to 162 ° C. When the melting point is lower than 150 ° C., the crystallinity is lowered, and mechanical strength such as bending strength at room temperature may be lowered. Note that most of the resin components are thermoplastic resins.

  The thermoplastic resin (a-1) melt index (MI; resin temperature 230 ° C., load 21.18 N) is preferably 100 to 250 g / 10 minutes, more preferably 100 to 150 g / 10 minutes. When the melt index of the thermoplastic resin is less than 100 g / 10 minutes, the reinforcing fibers may be difficult to open during molding. On the other hand, when the melt index of the thermoplastic resin exceeds 250 g / 10 minutes, the strength of the long fiber reinforced thermoplastic resin particles may be lowered.

  In order to adjust the melt index of the thermoplastic resin to the above range, for example, in the production of the thermoplastic resin, the molecular weight is adjusted by adjusting the hydrogen concentration introduced during the polymerization, etc. Alternatively, resins having different melt indexes may be blended or kneaded.

  The amount of the component soluble in o-dichlorobenzene at 90 ° C. measured by (a-2) cross-fractionation chromatography (CFC method) of the thermoplastic resin is preferably 1% by weight or less, more preferably 0.5% by weight. % Or less, particularly preferably 0.3% by weight or less. That the elution amount of 90 ° C. or less is 1% by weight or less means that the content of low crystallinity and low molecular weight components among the polymer components constituting the thermoplastic resin is low, and the thermoplastic resin is high. It means having heat resistance and strength.

  In the Japanese Patent Application No. 2008-074405, the present inventors have produced a thermoplastic resin using a Ziegler-based catalyst, but in a thermoplastic resin produced using a Ziegler-based catalyst, the elution amount at 90 ° C. Is about 3 to 10% by weight. That is, the thermoplastic resin produced using the Ziegler-based catalyst has a low crystallinity and a low molecular weight component content as compared with the thermoplastic resin according to the present invention, and is inferior in heat resistance and strength.

  Since the thermoplastic resin according to the present invention has a narrow molecular weight distribution (Mw / Mn) due to the characteristics of the metallocene catalyst, it is decomposed by adding a peroxide prior to the production of the long fiber reinforced thermoplastic resin particles. Since it is not necessary, the manufacturing process is efficient and there are almost no volatile organic compounds (VOC) generated in the decomposition process due to the addition of peroxide.

The molecular weight distribution (Mw / Mn) in terms of standard polypropylene measured by (a-3) gel permeation chromatography (GPC) of the thermoplastic resin is preferably less than 3.5, more preferably 1.5 to 3, particularly Preferably it is 2-2.7. When the molecular weight distribution (Mw / Mn) is larger than 3.5, the fiber opening property at the time of producing the long fiber reinforced thermoplastic resin particles deteriorates, and the surface of the molded body obtained by molding the long fiber reinforced thermoplastic resin particles In some cases, a lump-like appearance defect may occur. The number average molecular weight (Mn) is usually 2 × 10 ^{4 to} 12 × 10 ⁴ , preferably 3 × 10 ⁴ to 10 × 10 ⁴ , more preferably 4 × 10 ⁴ to 8 × 10 ⁴ . When the number average molecular weight (Mn) is in the above range, it is preferable from the viewpoint of achieving both ease of the fiber impregnation step and mechanical strength.

  The content of the thermoplastic resin is 20 to 70% by weight, preferably 25 to 67% by weight, more preferably 25 to 67% by weight, of the total of 100% by weight of the thermoplastic resin, modified polyolefin resin and reinforcing fiber. 30 to 65% by weight.

  The content of the thermoplastic resin is preferably 25 to 59% by weight, more preferably 30 to 57% by weight, and particularly preferably 35 to 55% by weight in a total of 100% by weight of the thermoplastic resin, the modified polyolefin resin and the reinforcing fiber. It is. When the content of the thermoplastic resin is less than 25% by weight, the impregnation into the fiber may be lowered. On the other hand, when the content of the thermoplastic resin exceeds 59% by weight, it may be difficult to produce pellets.

  Melting | fusing point measured with the differential scanning calorimeter of a thermoplastic resin is 150 degreeC or more, Preferably it is 150-163 degreeC, More preferably, it is 156-162 degreeC. When the melting point is lower than 150 ° C., the crystallinity is lowered, and mechanical strength such as bending strength at room temperature may be lowered.

  The melt flow rate (MFR; 230 ° C., 21.2 N load) of the thermoplastic resin is usually 100 to 250 g / 10 minutes, preferably 110 to 230 g / 10 minutes, more preferably 120 to 200 g / 10 minutes. When the melt flow rate (MFR) is in the above range, the dispersibility of the reinforcing fibers in the pellet is good, and it is preferable because the appearance of the pellet and a drop in impact strength are prevented.

<Modified polyolefin resin>
The modified polyolefin resin modified with the unsaturated carboxylic acid or derivative thereof according to the present invention has a functional group such as a carboxyl group or a carboxylic anhydride group in the polyolefin resin.

  The type of polyolefin resin to be modified is not particularly limited, but it is preferable to use the same thermoplastic resin as described above. For example, when a polypropylene resin is used as the thermoplastic resin, it is preferable to use a modified polyolefin resin as the modified polyolefin resin.

  Examples of the modified polyolefin resin include a modified propylene homopolymer, a modified propylene-α-olefin block copolymer, and a modified propylene-α-olefin random copolymer.

Graft modification and copolymerization can be used as a modification method of the polyolefin resin.
Examples of the unsaturated carboxylic acid used for modification include acrylic acid, methacrylic acid, maleic acid, nadic acid, fumaric acid, itaconic acid, crotonic acid, citraconic acid, sorbic acid, mesaconic acid, angelic acid and phthalic acid. It is done. Derivatives include acid anhydrides, esters, amides, imides and metal salts, such as maleic anhydride, itaconic anhydride, citraconic anhydride, nadic anhydride, phthalic anhydride, methyl acrylate, methacrylic acid. Examples thereof include methyl acid, ethyl acrylate, butyl acrylate, maleic acid monoethyl ester, acrylamide, maleic acid monoamide, maleimide, N-butylmaleimide, sodium acrylate and sodium methacrylate. Among these, unsaturated dicarboxylic acids and derivatives thereof are preferable, and maleic anhydride and phthalic anhydride are particularly preferable.

  The amount of modification of the unsaturated carboxylic acid or derivative thereof is 0.01 to 2% by weight, preferably 0.05 to 1.8% by weight, more preferably 0, out of a total of 100% by weight of the thermoplastic resin and the modified polyolefin resin. .1 to 1.5% by weight.

The carboxylic acid addition amount in the modified polyolefin resin is usually 0.1 to 14% by weight, preferably 0.8 to 8% by weight.
The modification of the polyolefin resin may be performed in advance prior to the production of the long fiber reinforced thermoplastic resin particles, or may be performed in the melt-kneading process during the production of the particles.

  For example, when the particles are preliminarily produced prior to the production of the particles, an appropriate amount of, for example, an acid-modified polyolefin resin is added to the thermoplastic resin when producing the long fiber reinforced thermoplastic resin particles.

  When it is carried out in the melt-kneading process, the thermoplastic resin, polyolefin resin and unsaturated carboxylic acid or derivative thereof are kneaded in an extruder using an organic peroxide, whereby the unsaturated carboxylic acid or its The derivative is graft copolymerized and modified.

  Examples of the organic peroxide include benzoyl peroxide, lauroyl peroxide, azobisisobutyronitrile, dicumyl peroxide, t-butyl hydroperoxide, α, α′-bis (t-butyl peroxide). Oxydiisopropyl) benzene, bis (t-butyldioxyisopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t- Butylperoxy) hexyne-3, di-t-butyl peroxide and cumene hydroperoxide.

  The content of the modified polyolefin resin is preferably 1 to 5% by weight, more preferably 1.5 to 3.5% by weight, in a total of 100% by weight of the thermoplastic resin, the modified polyolefin resin and the reinforcing fiber. When the content of the modified polyolefin resin is less than 1% by weight, the interfacial adhesion between the fiber and the finger may be lowered and the strength may be lowered. On the other hand, when the content of the modified polyolefin resin is more than 5% by weight, the overall molecular weight is lowered, and the strength may be lowered.

  Further, in the total 100% by weight of the thermoplastic resin and the modified polyolefin resin, the thermoplastic resin is preferably contained in a ratio of 75 to 99% by weight, and the modified polyolefin resin is preferably contained in a ratio of 1 to 25% by weight, and the thermoplastic resin is 85%. It is more preferable that the modified polyolefin resin is contained at a ratio of ˜98 wt% and 2 to 15 wt%.

<Reinforcing fiber>
The reinforcing fiber according to the present invention is not particularly limited, and examples thereof include organic fibers such as carbon and nylon, inorganic fibers such as basalt and glass fibers, and preferably glass fibers.

  Glass fibers such as E glass (Electrical glass), C glass (Chemical glass), A glass (Alkali glass), S glass (High strength glass), and alkali-resistant glass are melt-spun into filamentous fibers. Can be mentioned.

  In the present invention, glass long fibers are usually used. A continuous glass fiber bundle is used as a raw material for the long glass fiber, which is commercially available as glass roving. The average fiber diameter is usually 3 to 30 μm, preferably 13 to 20 μm, more preferably 16 to 18 μm, and the number of filament bundles is usually 400 to 10,000, preferably 1,000 to 6,000, More preferably, it is 3,000 to 5,000.

A plurality of fiber bundles can be bundled and used as disclosed in JP-A-6-114830.
The fiber length of the glass fiber in the long fiber reinforced thermoplastic resin particles is usually 4 to 10 mm, preferably 5 to 8 mm, and the fiber diameter is usually 10 to 20 μm, preferably 13 to 18 μm.

  The content of the reinforcing fiber is 30 to 80% by weight, preferably 40 to 70% by weight, more preferably 45 to 65% by weight, particularly preferably 100% by weight in total of the thermoplastic resin, the modified polyolefin resin and the reinforcing fiber. 45 to 60% by weight. When the content of the reinforcing fiber is less than 30% by weight, more specifically, less than 40% by weight, productivity may be lowered. On the other hand, when the content of the reinforcing fiber is more than 80% by weight, more specifically, more than 70% by weight, the amount of glass fiber increases, impregnation into the fiber may decrease, and the unopened glass fiber may increase. .

  The surface of the reinforcing fiber can be provided with a functional group by various surface treatment methods such as electrolytic treatment and sizing agent treatment. For the surface treatment, a sizing agent is preferably used, and a sizing agent containing a coupling agent is particularly preferably used. When the surface-treated reinforcing fiber is used, the adhesiveness with the thermoplastic resin is improved, and a molded article having good strength and appearance can be obtained.

Examples of the sizing agent include those containing a coupling agent as described in JP-A-2003-253563.
The coupling agent can be appropriately selected from conventionally known coupling agents such as so-called silane coupling agents such as aminosilane and epoxysilane and titanium coupling agents.

In addition to the coupling agent, the sizing agent preferably includes a resin emulsion for easy handling.
As the resin emulsion contained in the sizing agent, urethane-based, olefin-based, acrylic-based, nylon-based, butadiene-based, epoxy-based and the like can be used, and among these, urethane-based and olefin-based are preferably used. Here, the urethane-based sizing agent is usually an oil-modified type, a moisture-curing type, and a polyisocyanate obtained by polyaddition reaction of a diisocyanate compound and a polyhydric alcohol in a proportion of 50% by weight or more. Both a one-component type such as a block type and a two-component type such as a catalyst curing type and a polyol curing type can be used. Representative examples include the Bondic series and the Hydran series (both manufactured by DIC Corporation). On the other hand, as the olefin sizing agent, for example, a modified polyolefin resin modified with an unsaturated carboxylic acid or a derivative thereof can be used.

<Other ingredients>
In the long fiber reinforced thermoplastic resin particles of the present invention, conventionally known dispersants, lubricants, plasticizers, flame retardants, antioxidants (phenolic antioxidants, phosphorous oxidations) are within the scope of the present invention. Antioxidants and sulfur antioxidants), antistatic agents, copper damage inhibitors, light stabilizers, UV absorbers, crystallization accelerators (nucleating agents), foaming agents, crosslinking agents, antibacterial agents, etc. Additives, colorants such as pigments and dyes, carbon black, titanium oxide, bengara, azo pigments, anthraquinone pigments, particulate fillers such as phthalocyanine, talc, calcium carbonate, mica and clay, short fibers such as wollastonite Additives such as fillers and whiskers such as potassium titanate can be added.

<Long fiber reinforced thermoplastic resin particles>
The long fiber reinforced thermoplastic resin particles of the present invention containing the above-described thermoplastic resin, modified polyolefin resin, and reinforcing fibers can be produced by a known molding method such as a drawing method. A thermoplastic resin, a modified polyolefin resin, and a part of the reinforcing fiber may be separately melt-kneaded and then mixed (blended).

The shape of the long fiber reinforced thermoplastic resin particles is usually columnar.
The particle length of the long fiber reinforced thermoplastic resin particles is usually 4 to 10 mm, preferably 5 to 8 mm. When the particle length of the long fiber reinforced thermoplastic resin particles is less than 4 mm, the effect of improving rigidity, heat resistance and impact strength is low, and warping deformation may be increased. On the other hand, when the particle length of the long fiber reinforced thermoplastic resin particles exceeds 10 mm, molding may be difficult.

In the long fiber reinforced thermoplastic resin particles, it is preferable that reinforcing fibers having a fiber length of 4 to 10 mm are arranged substantially in parallel.
Since the long fiber reinforced thermoplastic resin particles of the present invention have a high aspect ratio of reinforcing fibers in the particles, a molded product obtained using the particles has high strength.

  The long fiber reinforced thermoplastic resin particles are obtained by guiding roving of thousands of reinforcing fibers to an impregnation die and melting a thermoplastic resin and a modified polyolefin resin (hereinafter also simply referred to as “molten resin”) between filaments. After impregnating uniformly, it can be easily obtained by cutting to the required length.

  For example, in the impregnation die provided at the tip of the extruder, the molten resin is supplied from the extruder, while the continuous glass fiber bundle is allowed to pass through, and the glass fiber bundle is impregnated with the molten resin, and then drawn through a nozzle. A method of pelletizing to the required length is taken. Further, a method may be used in which a polyolefin resin and an unsaturated carboxylic acid or an anhydride thereof are dry-blended using an organic peroxide, introduced into a hopper of an extruder, and supplied while simultaneously modifying.

  The method for impregnation is not particularly limited, and a method in which roving is passed through a resin powder fluidized bed and then heated above the melting point of the resin (Japanese Patent Laid-Open No. Sho 46-4545), using a crosshead die. Method of impregnating molten fiber with reinforcing fiber roving (Japanese Patent Laid-Open Nos. 62-60625, 63-1332036, 63-264326 and 1-208118) A method of mixing resin fibers and rovings of reinforcing fibers and then impregnating the resin by heating above the melting point of the resin (Japanese Patent Laid-Open No. 61-118235), arranging a plurality of rods inside the die, A method in which rovings are wound in a zigzag manner on a sheet and opened, and impregnated with a molten resin (Japanese Patent Laid-Open No. 10-264152), and passed between a pair of opened pins without contacting the pins Such method (WO 97/19805 pamphlet), any method can be used.

  Further, in the process of melting the resin, an extruder having two or more feed portions may be used, and the decomposition agent may be charged from the top feed and another resin may be charged from the side feed. At this time, as a decomposing agent, for example, in the case of a polypropylene resin, an organic peroxide is preferable.

Two or more extruders (extruding sections) may be used, and at least one of them may be charged with the decomposition agent.
Furthermore, a resin, an unsaturated carboxylic acid or a derivative thereof, and a decomposing agent may be added to at least one place of the extruder.

The long fiber reinforced thermoplastic resin particles obtained as described above were sealed from 25 g long fiber reinforced thermoplastic resin particles in a 20 L SUS chamber and left at 65 ° C. for 1 hour. the amount of acetaldehyde dissipated is, 3.0 [mu] g / m ³ or less, preferably 2.8μg / m ³ or less, more preferably 2.7μg / m ³ or less.

  As described above, the thermoplastic resin according to the present invention has a narrow molecular weight distribution (Mw / Mn) depending on the characteristics of the metallocene catalyst used at the time of production. Therefore, prior to producing the long fiber reinforced thermoplastic resin particles, the thermoplastic resin is used. There is no need to add peroxides to decompose them. The reason why the amount of aldehyde emitted from the long fiber reinforced thermoplastic resin particles of the present invention is small is that no volatile low molecular weight component accompanying decomposition by peroxide is generated.

  The long fiber reinforced thermoplastic resin particles of the present invention can be efficiently produced because there is no need to remove volatile components (such as VOC) that are generated as the thermoplastic resin is decomposed.

As in Japanese Patent Application No. 2008-074405, a thermoplastic resin produced using a Ziegler-based catalyst is produced using a Ziegler-based catalyst, and therefore has a wide molecular weight distribution (Mw / Mn) and a low molecular weight component. Therefore, prior to the production of long fiber reinforced thermoplastic resin particles, it is necessary to add a peroxide to perform decomposition. For this reason, when the amount of aldehyde was analyzed about the pellet obtained from the thermoplastic resin manufactured using the Ziegler catalyst, 6.7 microgram / m < ³ > (25g long fiber reinforced thermoplastic resin particle | grains was measured by the method mentioned above. Sometimes the amount of acetaldehyde released from the pellets is 6.7 μg / m ³ ), and it is clear that the amount of aldehyde emitted is larger than the long fiber reinforced thermoplastic resin particles of the present invention.

  The molded body obtained by using the long fiber reinforced thermoplastic resin particles of the present invention is excellent in appearance because the reinforcing fibers are sufficiently opened. In addition, since the length of the reinforcing fiber is maintained for a long time, the physical properties equivalent to or higher than those of the conventional product can be maintained.

〔Example〕
EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not limited to these Examples.
Various parameters in the table were measured by the following methods.

[Melt index (MI)]
Based on JIS K 7210-1999, the measurement was performed under the conditions of a resin temperature of 230 ° C. and a load of 21.18 N.

[Amount of component soluble in o-dichlorobenzene at 90 ° C.]
Measurement was performed using a cross-fractionation chromatograph (CFC).
Analysis of components soluble in o-dichlorobenzene at each temperature was performed by a cross-fractionation chromatograph (CFC). CFC was measured under the following conditions using the following apparatus equipped with a temperature rising elution fractionation (TREF) part for performing composition fractionation and a GPC part for performing molecular weight fractionation, and the amount at each temperature was calculated.
Measuring device: CFC T-150A type, manufactured by Mitsubishi Yuka Co., Ltd.
Column: Shodex AT-806MS (× 3)
Dissolved solution: o-dichlorobenzene Flow rate: 1.0 ml / min
Sample concentration: 0.3 wt% / vol% (with 0.1% BHT)
Injection volume: 0.5 ml
Solubility: Complete dissolution Detector: Infrared absorption detection method, 3.42μ (2924 cm ^-1 ), NaCl plate Elution temperature: 0 to 135 ° C, 28 fractions
0, 10, 20, 30, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 94, 97, 100, 103, 106, 109, 112, 115, 118, 121, 124, 127, 135 (℃)

For details of the measurement, the sample was heated at 145 ° C. for 2 hours to dissolve, held at 135 ° C., then cooled to 0 ° C. at 10 ° C./hour, and further held at 0 ° C. for 60 minutes to coat the sample. It was. The temperature rising elution column capacity is 0.83 ml, and the pipe capacity is 0.07 ml. The detector used was an infrared spectrometer MIRAN 1A CVF type (CaF ₂ cell) manufactured by FOXBORO, and infrared light of 3.42 μm (2924 cm ⁻¹ ) was detected in an absorbance mode setting with a response time of 10 seconds. The elution temperature was divided into 28 fractions from 0 to 135 ° C. All temperature indications are integers. For example, the elution fraction at 94 ° C. indicates a component eluted at 91 to 94 ° C. The molecular weight of components that were not coated even at 0 ° C. and the fraction eluted at each temperature were measured, and the molecular weight in terms of polypropylene was determined using a general-purpose calibration curve. The SEC temperature is 135 ° C., the internal standard injection amount is 0.5 ml, the injection position is 3.0 ml, and the data sampling time is 0.50 seconds. Data processing was performed with the analysis program “CFC data processing (version 1.50)” attached to the apparatus.

[Number average molecular weight (Mn), weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)]
It measured using the gel permeation chromatograph (GPC).
The molecular weight and molecular weight distribution were measured using GPC-150C Plus manufactured by Waters as follows. The separation columns were TSKgel GMH6-HT and TSK gel GMH6-HTL, the column size was 7.5 mm in inner diameter and 600 mm in length, the column temperature was 140 ° C., and o-dichlorobenzene (Wako Pure Chemical Industries) was used as the mobile phase. (Pharmaceutical industry) and BHT (Wako Pure Chemical Industries) 0.025% by weight as an antioxidant, moved at 1.0 ml / min, the sample concentration was 0.1% by weight, and the sample injection volume was 500 microliters A differential refractometer was used as a detector. Standard polystyrene is converted to PP using a general-purpose calibration method using Tosoh Corporation for molecular weights of Mw <1000 and Mw> 4 × 10 ⁶ , and pressure chemicals for 1000 ≦ Mw ≦ 4 × 10 ^6. did. The Mark-Houwink coefficients of PS and PP are the values described in the literature (J. Polym. Sci., Part A-2, 8, 1803 (1970), Makromol. Chem., 177, 213 (1976)), respectively. Was used.

[Measurement of the amount of VOC (acetaldehyde)]
The measuring method is as follows.
(I) A 20 L volume SUS chamber is sealed and heated to 65 ° C.
(Ii) Collect chamber blank after 1 hour.
(Iii) After returning to room temperature, long fiber reinforced thermoplastic resin particles are charged and purged with clean air.
(Iv) The chamber is sealed and warmed again to 65 ° C.
(V) After leaving to be sealed for 1 hour, clean air is introduced again, and air containing the gas emitted from the long fiber reinforced thermoplastic resin particles is collected at a sampling flow rate of 200 mL / min for 50 minutes.

A 2,4-DNPH cartridge was used as the adsorbent.
(Vi) 10 L of the collected gas is dissolved with a solvent, and aldehydes contained in the emitted gas are analyzed by high performance liquid chromatography (HPLC).

In addition, although formaldehyde was also detected accompanying aldehyde, the amount of formaldehyde contained in the collected emitted gas was less than 2 μg / m ³ when measured on 25 g of the long fiber reinforced thermoplastic resin particles.

[Melting point (Tm)]
The measurement was performed using a differential scanning calorimeter (DSC, manufactured by Perkin Elmer). Here, the endothermic peak at the third step was defined as the melting point (Tm).
(Sample preparation conditions)
Molding method: Press mold: Thickness 0.2mm (sample is sandwiched between aluminum foils, press mold using mold)
Molding temperature: 240 ° C (heating temperature 240 ° C)
Press pressure: 300 kg / cm ² , press time: 1 minute,
After press molding, the sheet is cooled with ice water, and about 0.4 g of the sheet is enclosed in the following measurement container: DSC PANS 10 μl BO-14-3015
DSC COVER BO14-3003
(Measurement condition)
First step: The temperature is raised to 240 ° C. at 10 ° C./min and held for 10 minutes.
Second step: The temperature is lowered to 30 ° C. at 10 ° C./min.
Third step: The temperature is raised to 240 ° C. at 10 ° C./min.

[Bending test]
(1) Testing machine: Bend testing machine AGS-10KND manufactured by Shimadzu Corporation
(2) Test piece size: L × W × t = 120 × 10 × 4 (mm)
(3) Test conditions: temperature 23 ° C., span 80 mm, test speed 2 mm / min

<Production Example 1> Production of thermoplastic resin (mPP-1) / brand name A-1 (1) Production of solid catalyst carrier 300 g of SiO ₂ was sampled in a 1 L branch flask, and 800 ml of toluene was put into a slurry. Next, the solution was transferred to a 5 L four-necked flask, and 260 mL of toluene was added. 2830 mL of a methylaluminoxane (hereinafter also referred to as “MAO”)-toluene solution (10 wt% solution) was introduced. The mixture was stirred at room temperature for 30 minutes. The temperature was raised to 110 ° C. over 1 hour, and the reaction was carried out for 4 hours. After completion of the reaction, it was cooled to room temperature. After cooling, the supernatant toluene was extracted and replaced with fresh toluene until the substitution rate reached 95%.

(2) Production of solid catalyst (support of metal catalyst component on carrier)
[3- (1 ', 1', 4 ', 4', 7 ', 7', 10 ', 10'-octamethyloctahydrodibenzo [b, h] fluorenyl in a 5 L four-necked flask in a glove box ) (1,1,3-trimethyl-5-t-butyl-1,2,3,3a-tetrahydropentalene)] zirconium dichloride was weighed in 2.0 g. The flask was taken out, 0.46 liters of toluene and 1.4 liters of MAO / SiO ₂ / toluene slurry prepared in (1) were added under nitrogen, and the mixture was stirred for 30 minutes to carry. The resulting [3- (1 ′, 1 ′, 4 ′, 4 ′, 7 ′, 7 ′, 10 ′, 10′-octamethyloctahydrodibenzo [b, h] fluorenyl) (1,1,3- Trimethyl-5-t-butyl-1,2,3,3a-tetrahydropentalene)] zirconium dichloride / MAO / SiO ₂ / toluene slurry was 99% substituted with n-heptane to give a final slurry volume of 4 .5 liters. This operation was performed at room temperature.

(3) Production of prepolymerization catalyst 404 g of the solid catalyst component prepared in (2) above, 218 mL of triethylaluminum, and 100 L of heptane were charged into an autoclave equipped with a stirrer with an internal volume of 200 L, and maintained at an internal temperature of 15 to 20 ° C. 1212 g was charged and reacted with stirring for 180 minutes. After completion of the polymerization, the solid component was precipitated, and the supernatant was removed and washed with heptane twice. The obtained prepolymerized catalyst was resuspended in purified heptane and adjusted with heptane so that the solid catalyst component concentration was 4 g / L. This prepolymerized catalyst contained 3 g of polyethylene per 1 g of the solid catalyst component.

(4) Main polymerization In a jacketed circulation tubular polymerizer with an internal capacity of 58 L, propylene is 40 kg / hour, hydrogen is 5 NL / hour, and the catalyst slurry produced in (3) is 0.8 g / hour as a solid catalyst component, triethylaluminum. 4 ml / hour was continuously supplied, and polymerization was performed in a full liquid state without a gas phase. The temperature of the tubular reactor was 30 ° C., and the pressure was 3.2 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 1000 L and further polymerized. To the polymerization reactor, propylene was supplied at a rate of 45 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.25 mol%. Polymerization was performed at a polymerization temperature of 72 ° C. and a pressure of 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. To the polymerization vessel, propylene was supplied at 10 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.25 mol%. Polymerization was performed at a polymerization temperature of 71 ° C. and a pressure of 3.0 MPa / G.

After vaporizing the resulting slurry, gas-solid separation was performed to obtain a propylene homopolymer. The resulting propylene homopolymer was vacuum dried at 80 ° C.
The resulting polypropylene homopolymer (mPP-1) had a weight average molecular weight (Mw) of 93,000, a number average molecular weight (Mn) of 42,000, a molecular weight distribution (Mw / Mn) of 2.2, a melt index ( MI) was 165 g / 10 min, the amount of components soluble in o-dichlorobenzene at 90 ° C. was 0.2% by weight, and the melting point (Tm) was 156 ° C.
The results are shown in Table 1.

<Production Example 2> Production of Thermoplastic Resin (mPP-2) / Brand Name A-2 In Production Example 1, the same procedure as in Production Example 1 was repeated except that the polymerization method was changed to the method shown below. mPP-2) was produced.

(1) Main polymerization In a jacketed circulation tubular polymerizer with an internal capacity of 58 L, propylene is 40 kg / hour, hydrogen is 5 NL / hour, and the catalyst slurry produced in Production Example 1 (3) is 1.0 g / hour as a solid catalyst component. Then, 4 ml / hour of triethylaluminum was continuously fed, and polymerization was carried out in a full liquid state without a gas phase. The temperature of the tubular reactor was 30 ° C., and the pressure was 3.2 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 1000 L and further polymerized. To the polymerization reactor, propylene was supplied at 45 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.24 mol%. Polymerization was performed at a polymerization temperature of 72 ° C. and a pressure of 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. To the polymerization vessel, propylene was supplied at 10 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.24 mol%. Polymerization was performed at a polymerization temperature of 71 ° C. and a pressure of 3.0 MPa / G.

After vaporizing the resulting slurry, gas-solid separation was performed to obtain a propylene homopolymer. The resulting propylene homopolymer was vacuum dried at 80 ° C.
The resulting polypropylene homopolymer (mPP-2) had a weight average molecular weight (Mw) of 104,000, a number average molecular weight (Mn) of 45,000, a molecular weight distribution (Mw / Mn) of 2.3, a melt index ( MI) was 115 g / 10 min, the elution amount at 100 ° C. or lower was 0.1% by weight, and the melting point (Tm) was 156 ° C.
The results are shown in Table 1.

<Manufacture example 3> Manufacture of a thermoplastic resin (mPP-3) It carried out with the following method using the solid catalyst support manufactured by manufacture example 1 (1).
(1) Production of solid catalyst (support of metal catalyst component on support)
In a glove box, 2.0 g of diphenylmethylene (3-t-butyl-5-methylcyclopentadienyl) (2,7-t-butylfluorenyl) zirconium dichloride was weighed in a 5 L four-necked flask. The flask was taken out, 0.46 liters of toluene and 1.4 liters of MAO / SiO ₂ / toluene slurry prepared in Production Example 1 (1) were added under nitrogen, and the mixture was stirred for 30 minutes to carry. The obtained diphenylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (2,7-tert-butylfluorenyl) zirconium dichloride / MAO / SiO ₂ / toluene slurry was 99% in n-heptane. Substitution was performed and the final slurry volume was 4.5 liters. This operation was performed at room temperature.

(2) Production of prepolymerization catalyst 404 g of the solid catalyst component prepared in (1) above, 218 mL of triethylaluminum, and 100 L of heptane were charged into an autoclave equipped with a stirrer with an internal volume of 200 L, and maintained at an internal temperature of 15 to 20 ° C. Was reacted with stirring for 180 minutes. After completion of the polymerization, the solid component was precipitated, and the supernatant was removed and washed with heptane twice. The obtained prepolymerized catalyst was resuspended in purified heptane and adjusted with heptane so that the solid catalyst component concentration was 4 g / L. This prepolymerized catalyst contained 3 g of polyethylene per 1 g of the solid catalyst component.

(3) Main polymerization In a tubular polymerization vessel having an internal volume of 58 L, propylene is 40 kg / hour, hydrogen is 5 NL / hour, the catalyst slurry produced in Production Example 3 (2) is 1.7 g / hour as a solid catalyst component, and triethylaluminum 4 ml. / Time was continuously supplied, and polymerization was performed in a full liquid state without a gas phase. The temperature of the tubular reactor was 30 ° C., and the pressure was 3.2 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 1000 L and further polymerized. To the polymerization reactor, propylene was supplied at 45 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.20 mol%. Polymerization was performed at a polymerization temperature of 72 ° C. and a pressure of 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. Propylene was supplied to the polymerization vessel at a rate of 10 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.20 mol%. Polymerization was performed at a polymerization temperature of 71 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 L and further polymerized. Propylene was supplied to the polymerization vessel at a rate of 10 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.20 mol%. Polymerization was performed at a polymerization temperature of 69 ° C. and a pressure of 3.0 MPa / G.

  The resulting polypropylene homopolymer (mPP-3) has a weight average molecular weight (Mw) of 94,000, a number average molecular weight (Mn) of 41,000, a molecular weight distribution (Mw / Mn) of 2.3, and a melt index (MI). Was 165 g / 10 min, and the amount of the component soluble in o-dichlorobenzene at 90 ° C. was 6% by weight.

[Example 1]
Long fiber reinforced thermoplastic resin particles were manufactured using the pellet manufacturing apparatus shown in FIG.
In FIG. 1, 10 is a die, 20 is an extruder that supplies molten resin to the die 10, 30 is a roll of a fiber bundle F, and 40 is a tension roll group that applies a constant tension to the fiber bundle F drawn into the die 10. , 50 is a cooling means for cooling the molten resin-impregnated fiber bundle drawn from the die 10, 60 is a fiber bundle pulling roll, and 70 is a long fiber reinforced thermoplastic by cutting the drawn molten resin-impregnated fiber bundle. It is a pelletizer used as resin particles. In this apparatus, three independent fiber bundles F are simultaneously impregnated with molten resin.
Specific manufacturing conditions are as follows.

-Die: Attached to the tip of a 50 mφ extruder, and four rods are arranged in a straight line at the impregnation part.-Fiber bundle: Glass roving bundled with 4000 glass fibers having a fiber diameter of 16 µm surface-treated with aminosilane-Preheating temperature: 200 ° C
Thermoplastic resin and modified polyolefin resin: mPP-1 (propylene homopolymer) and PP-2 (maleic anhydride modified polypropylene, maleic anhydride addition amount 2% by weight, H-1100P, Prime Polymer Co., Ltd. shown in Table 1 The product is blended so that the composition ratio shown in Table 2 is obtained, and the melting and melting temperature is 280 ° C.
・ Rod: Four 6mm (diameter) x 3mm (length)
・ Inclination angle: 25 degrees

Under the above conditions, the tension roll group adjusts the amount of the fiber bundle and feeds it into the die for impregnation, and then pulls out from the die and cools to produce long fiber reinforced thermoplastic resin particles having a particle length of 6 mm with a pelletizer. .
Test pieces were prepared from the long fiber reinforced thermoplastic resin particles using an injection molding machine.
(Injection molding conditions)
(1) Molding machine: FANUC α100B (full flight screw)
(2) Mold: ISO-compatible tensile dumbbell (two sets)
(3) Molding temperature: 250 ° C / Die temperature: 45 ° C
Table 2 shows the results of melting point (Tm), bending strength and bending elastic modulus measured for this test piece.

[Example 2]
In Example 1, long fiber thermoplastic resin particles were produced in the same manner as in Example 1 except that mPP-2 shown in Table 1 was used as the thermoplastic resin.

[Comparative Example 1]
In Example 1, long-fiber thermoplastic resin particles were produced in the same manner as in Example 1 except that mPP-3 shown in Table 1 was used as the thermoplastic resin, and an injection-molded test piece was produced.

[Comparative Example 2]
In Example 1, long-fiber thermoplastic resin particles were produced in the same manner as in Example 1 except that PP-1 shown in Table 1 was used as the thermoplastic resin, and an injection-molded test piece was produced.

  The long fiber reinforced thermoplastic resin particles of the present invention are used for automobile parts (front end, fan shroud, cooling fan, engine under cover, engine cover, radiator box, side door, slide door, back door inner, back door outer, outer plate. , Fenders, roof rails, door handles, door trims, luggage boxes, wheel covers and handles), motorcycle and bicycle parts (luggage boxes, handles and wheels), housing-related parts (hot water flush toilet parts, bathroom parts, bathtub parts, chair legs , Valves and meter boxes), washing machine parts (such as bathtubs and balance rings), fans for wind power generators, power tool parts, mower handles and hose joints.

10 Die 20 Extruder 30 Roll of Fiber Bundle F 40 Tension Roll Group 50 Cooling Means 60 Drawer Roll 70 Pelletizer

Claims (5)

A thermoplastic resin produced using a metallocene catalyst,
A long fiber reinforced thermoplastic resin particle comprising a modified polyolefin resin modified with an unsaturated carboxylic acid or a derivative thereof, and reinforcing fibers, and satisfying the following requirements (1) to (5).
(1) The amount of modification of the unsaturated carboxylic acid or derivative thereof is 0.01 to 2% by weight in a total of 100% by weight of the thermoplastic resin and the modified polyolefin resin.
(2) The thermoplastic resin and the modified polyolefin resin are contained in a total of 20 to 70% by weight in the total 100% by weight of the thermoplastic resin, the modified polyolefin resin and the reinforcing fiber.
(3) 30 to 80% by weight of reinforcing fiber is contained in 100% by weight of the total of the thermoplastic resin, modified polyolefin resin and reinforcing fiber.
(4) When 25 g of long fiber reinforced thermoplastic resin particles are sealed in a 20 L chamber and left at 65 ° C. for 1 hour, the amount of acetaldehyde released from the long fiber reinforced thermoplastic resin particles is 3.0 μg / m. ³ or less.
(5) The melting point of the resin component in the long fiber reinforced thermoplastic resin particles is 150 ° C. or higher.   2. The thermoplastic resin according to claim 1, wherein 75 to 99 wt% of the thermoplastic resin and 1 to 25 wt% of the modified polyolefin resin are contained in a total of 100 wt% of the thermoplastic resin and the modified polyolefin resin. Long fiber reinforced thermoplastic resin particles. The thermoplastic resin particles according to claim 1 or 2, wherein the thermoplastic resin satisfies the following requirements (a-1), (a-2), and (a-3).
(A-1) The melt index (MI; resin temperature 230 ° C., load 21.18 N) is in the range of 100 to 250 g / 10 minutes.
(A-2) The amount of components soluble in 90- ° C. o-dichlorobenzene measured by cross fractionation chromatography (CFC method) is 1% by weight or less.
(A-3) Molecular weight distribution (Mw / Mn) is less than 3.5.   The length according to any one of claims 1 to 3, wherein the thermoplastic resin is at least one polymer selected from a propylene homopolymer and a propylene-α-olefin random copolymer. Fiber reinforced thermoplastic resin particles.   The molded object obtained by shape | molding using the long fiber reinforced thermoplastic resin particle in any one of Claims 1-4.

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